DE2131706A1 - New monoazo dyes, their manufacture and use - Google Patents

Description

Lawyer File 21 25k June 25, 1971

New monoazo dyes, their manufacture and use. "

The present invention relates to new monoazo dyes of the formula

(1) Y-R-N-N-D-Y

wherein Y-R is a benzene or sulfonic acid group Naphthalene radical, Y-D the radical of a coupling component of the benzene series or the heterocyclic series, a Y. Hydrogen atom and the other Y one via an amino bridge, in particular via an amino bridge of the formula -NH- Triazine residue of the B'ormel

₀ c

IJ

109882/1696 oRtGtNAL inspected

mean, where A is a quaternized amino or hydrazine © -, group of formula. , -

^CH 3 CH ₀ -CH ₀ CH

-Ν — CH, -N y , -N — CH ₂ -CH ₂ —N or -NH H ^ Χ "

represents wherein X is an anion. The present invention is particularly concerned with

Monoazo dyes of the formula

CH ₀ -CH ₀ N SO "H / 2 2 \ // \ / w 3

0 N-C C-NH- ^ i

. ^X CH _O -CH, / I II / ^{> c / s} iT = N-Pz

(3) - ^ NN (SO_H) _Ί

^ _0/3 n-1

and monoazo dyes of the formula

B ZN = N Λ / Ν CH ₀ -CH

C C -N

(4) I II

NN

In these two formulas, the symbols Pz denote a 5-pyrazolone radical bonded to the azo bridge in the 4-position, η denote the numbers 1 and 2, B a low molecular weight alkoxy group, a low molecular weight alkyl group or a hydrogen atom, E a low molecular weight alkoxy group, a low molecular weight one

109882/16 96

Alkyl group, a low molecular acylamino group or a hydrogen atom, Z a sulfobenzene or sulfonaphthalene, esp. Trisulfonaphthylrest and A in the explanation of the Formula (2) given quaternary substituents. Acyl means in particular the radical of an aromatic, heterocyclic one or especially low molecular weight aliphatic carboxylic acid or a carbonic acid monoester or optionally N-alkylated Carbonic acid monoamids.

Particularly valuable among the dyes of the formula (3) are those which also have a Have sulfonic acid group and among those of the formula (4) those in which B is a hydrogen atom, E is an acetylamino or H N-CO-NH group and Z is one in ß-position on the azo bridge bound di- or trisulfonaphthy! group mean.

The inventive preparation of the new dyes is characterized in that either a) a diazo compound from an amine of the formula

(5) YR-NH ₂ or (5a) CH-CH ₀ N

κ 2 2 \ // \

0 NC C-NH \ - I or

I Ι

N N

-Nj /

(5b) Z-NH ₀

10 9 0 82/1696

in which the symbols Y, R, Z, A and η have the meaning given above, with a coupling component of the formula

(6) HD-Y or (6b) H-Pz or

^{(6c) Η} ~~ ίΧ / A / V ⁰ V

—C C N

I π N /

NN

B, E, A ₃ / couples, in which the symbols / D, Y and Pz are those given above

Have meaning or that one

1 0 9 8 8 2/1 (i 9 n

b) an azo dye of the formula (l) given above or (3) or (4) ,, where all symbols with the exception of the symbols A have the meaning given above and A represents a chlorine or bromine atom, with one of the following compounds

pil

N — CH “, N>, N — CH — CH ₀ —N, N — NH-3 \ —X \ 2 2 / χ

^X CH -CH ₀ / X) H

implements.

The following amines, for example, can be used as diazo components which can be used in the preparation by coupling in question:

l-aminobenzene-2-sulfonic acid, l-aminobenzene-2,5-disulfonic acid, l-amino-4-methylbenzene-2-sulfonic acid _ί 1-amino-5-acetylaminobenzene-2-sulfonic acids l-amino-4-acetylaminobenzene-2 sulfonic acid, l-amino-4-nitrobenzene-2-sulfonic acid, l-amino-6-methylbenzene-2,4-disulfonic acid, 1-amino-4-methoxybenzene-2-sulfonic acid, l-amino-4,6-dimethyl ! Benzene-2-sulfonic acid, l-amino-5-fluorobenzene-2-sulfonic acid, l-aminobenzene-2,4,6-trlsulfonic acid, 2-aminonaphthalene-4,8- or 5j7-disulfonic acid, 2-aminonaphthalene-4, 6,8- or 3,5 * 7-trisulfonic acid, l-aminonaphthalene-5,6-disulfonic acid,

109882/1696

-f- ■■■

l-aminobenzene-2,4-disulfonic acid,

1-amino-4-chlorobenzene-2-sulfonic acids

also l-aminobenzene-2-sulfonic acids, which already have a
2-morpholine-l, j5j contain 5-triazinyl radical of the type indicated, such as:

1-Amino-5- [2 ^T -morpholino) - 4 ^r -chlor tr la ζ in-1 '., 3'>5'-γ1-6'] -aminobenzene-2-sulfonic acid,

as well as other condensation products that can be obtained from, for example
1,4-diaminobenzene-2-sulfonic acid or from

1,4-diaminobenzene-2,5-disulfonic acid or. from l, 3 ~ Diarninoben2o * l> "· ' 4,6-disulfonic acid by reaction with cyanuric chloride or bromide and morpholine, as well as compounds of the formula

0 N-C C -C -NH-R-MH

(7) ²² NN

where R and A are the same as in the explanation of the formulas (1) and '(2)
have given meaning.

As coupling components of the above
Formulas (6) and (6b), according to the present method
which can be used as starting materials are, for example: a) when using diazo components which contain the characteristic triazine group:
Barbituric acid,
2,4-dihydroxyquinoline,

109882/1696

3-methyl-5-pyrazolone,
l-phenyl - ^ - methyl or

3-carboxy-5-pyrazolone,

1- (2'-chlorophenyl) - ^ - methyl-5-pyrazolon-5 ^l -sulfonic acid, 1- (2 ^f , 5 ^t -dichloroplienyl) -3-methyl-5-pyrazolone-4 ^I -sulfonic acid.

b) when using diazo components without a triazine group: Anisidine, cresidine, toluidine, xylidine, 3-acetylaminoaniline, 3-ureidoaniline.

In case b), the dyes obtained by condensation with cyanuric chloride or bromide, morpholine and. the tertiary amines, or dimethylhydrazine mentioned in the ^invention: converted isse dyes of the formula (l) or (4).

The amines used in the present process are diazotized by methods known per se e.g. with the help of hydrochloric acid and sodium nitrite. The coupling is also carried out by methods known per se, in two ways in weakly acidic to neutral, e.g. in acetic acid medium.

Djc starting dyes of the formula (I) used in the preparation by condensation, where RY Z and Z _{1 have} the specified ¹ X (Ie:! '^ ^- ; where jfdoch the one specified in formula (P.) ] -, ■■ : · 1 · Λ ■ '■ \) j> - ■ - or Brora ^ -oi'

1 (I iJ V 'i <I \ (. Ü C

BATH ORIGINAL

represents, can be produced according to methods known per se. can be provided, e.g. by coupling the corresponding diazo and coupling components or by condensation of cyanuric chloride or cyanuric bromide in any order on the one hand with the corresponding dyes and on the other hand with morpholine.

The inventive condensation of the thus obtained Starting azo dyes with the tertiary amino. or the hydrazino compound is conveniently carried out through Stir the two reactants together in an aqueous or aqueous organic medium at a temperature of 0-100. Instead of the free bases of the tertiary amines, they can also be inorganic or organic Acid-deriving salts can be used.

The dyes obtained according to the invention are preferably isolated at low temperatures by salting out and filtering. The isolated dyes can, if necessary, after the addition of coupage agents or Stabilizers are dried; drying is preferably carried out at temperatures that are not too high and made under reduced pressure. By spray drying the entire preparation mixture, one can in In certain cases, produce dry preparations directly, i.e. without intermediate isolation of the dyes. According to this method

109882/169 6

will receive new valuable dry preparations that are suitable for the production of stock solutions or parbaths and especially of printing pastes.

The dyes obtained by the specified process are new. They are valuable links to that for dyeing and especially for printing a wide variety of materials, especially polyhydroxylated Materials with a fibrous structure, such as cellulose-containing materials, both synthetic fibers, e.g. from regenerated Cellulose or natural materials, e.g. cellulose, linen or especially cotton are suitable.

After dyeing or printing is recommended as complete a removal of the unfixed dye as possible. For this purpose the colorations and Prints thoroughly rinsed with warm and cold water and a soaping process in the presence of non-ionic dispersing agents. and / or subjected to wetting agents.

• -

The dyeings or prints obtained with the dyes according to the application are generally distinguished by good lightfastness and, above all, very good wetfastness. The necessary fixing times are relatively short and the dye components that are not fixed to the fiber can be washed out easily. In particular, the printing pastes obtained with the new dyes show good stability.

109882/1696

The dyes of the formula (I) or (3) or (4) obtained according to the invention are particularly valuable Printing on naphtholized or non-naphtholized goods. They can be fixed without a steaming process. On naphtholized They can be used alongside or in combination with diazo salts. For non-naphtholized goods it is - ~ We recommend replacing the naphthol primer that is no longer necessary with a pre-treatment with soda and urea. The fixation of the prints then takes place as usual in the technique of so-called "Africa prints" on drying drums or on very efficient attic.

109882/1696

In the following examples, unless otherwise stated, the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in degrees Celsius. The dyes formulated as salts in the formulas can optionally also present as internal salts, the quaternized amino or hydrazino radical being the cation and one aromatic bonded -SO ^ group forms the anion.

109882/1696

Example 1.

268 parts of 1,4-phenylenediamine-2,5-disulfonic acid become reacted with 190 parts of cyanuric chloride, with neutralization the released hydrochloric acid with 90 parts of sodium bicarbonate.

87 parts of morpholine are then added dropwise at 10-20 ° so that the pH is between 6-7. After finished The hydrochloric acid released is neutralized by adding morpholine by adding 100 parts of jJO ^ iger sodium hydroxide solution.

it /

The product thus obtained is without / to isolate on

Parts of 1-phenyl-3-methyl-5-pyrazolone-4'-sulfonic acid coupled. The dye is deposited by adding sodium chloride.

287 parts of this dye are in 2000 parts of water at 45 ° -50 ° with 147 parts of a 40% aqueous trimethylamine solution offset so that the pH is between 8.0 and 8.5. The dye is isolated by salting out with common salt and the dye is obtained in this way, which is the free acid of the formula

C-KH

SO.

-N = N-C = C

"Θ

is equivalent to

He delivers washable yellow prints on cotton.

109882/1696

Are instead of 268 parts 1,4-phenylenediamine-2,5-disulfonic acid 188 parts 1,4-phenylenediamine-2-sulfonic acid were used and otherwise proceed as indicated in Sections 1 to 4, the dye obtained is the one below as the free acid Has constitution and which gives yellow prints of excellent washfastness on cellulose material.

Dyes on cotton yellow prints with similar properties supply, is obtained by proceeding as indicated in Sections 1 to 5, but instead of the trimethylamine solution

at 45-55 ° / 45 to 50 ° an equimolar amount of pyridine / or an equimolar amount

Amount of N, N, dimethylhydrazine at room temperature or an equimolar

at room temperature / amount of diazabicyclo- (2,2,2) -octane / is added dropwise.

Dyes that give yellow prints with similar properties on cotton are also obtained by proceeding as described in Sections 1 to 6, but instead of the phenyl-5-methyl-5-pyte ^> azolon-4 ^f -sulfonic acid ^(t 2-chlorophenyl) -3-methyl-5-pyrazolone-5'-sulfonic acid equimolar amount of 1- or 'l-phenyl-3-niethyl-5-pyi'azolon-2 _J 5-disulfonic acid used.

109882/1696

Example 2.
464 parts of the dye made by coupling

diazotized 2-aminonaphthalene-4,8-disulfonic acid on mono water / acetyl-m-phenyldiamine are reacted in 4000 parts / at 0-5 with 190 parts of cyanuric chloride, the released Hydrochloric acid is neutralized with 100 parts of 30% sodium hydroxide solution. Then 87 parts of morpholine are added dropwise at 30-35 ° so that that the pH is between 6.5 and 7. Without isolating the dye, 95 parts of trimethylamine hydrochloride are added 400 parts of water are added at room temperature, the pH is adjusted to 10-11 with sodium hydroxide solution and the mixture is stirred for 1 hour at room temperature. The pH is then adjusted to 7 with hydrochloric acid.

The dyestuff is isolated by salting out with common salt, in this way the dyestuff is obtained, which is the free acid of the formula

N (CH),

SO,

-N = N-

NH-C

^K OH GH CN 0

NHCOCH

and with which you can print cotton in washable yellow tones.

If you use 5 ^ 5 parts of the starting dyes Dye prepared by coupling diazotized 2-aminonaphthalene-3,6,8-trisulfonic acid on 3-aminophenylurea and proceed as indicated in Sections 1 to 2, so

109882/1696

one obtains the dye of the following constitution, the also gives golden yellow prints of excellent washfastness on cotton.

B (

N N

NH-C C-N

CH ₀ -CH / 2

NHCONH.

Wild instead of trimethylamine an equimolar

at room temperature/
Amount of N, N-dimethylhydrazine / or diaza-bicyclo- (2,2,2) -octane

used for quaternization at room temperature and otherwise
if you proceed as indicated in Sections 1 to J5, dyes are obtained which produce yellow prints with similar properties on cotton.

109882/1696

Printing specification.

2 parts of dye are added to 100 parts of a stock thickener containing 45 parts with rapid stirring 5 $ sodium alginate thickener,} 2 parts water, 20 parts Urea, 1 part of sodium m-nitrobenzenesulfonate and 2 parts of sodium bicarbonate, sprinkled.

The printing paste thus obtained is used to print a cotton fabric on a roller printing machine and steams the resulting printed fabric for 1 to 2 minutes at 100 in saturated steam. The printed fabric will then rinsed thoroughly in cold and hot water, whereby the non-chemically fixed parts are very easy remove from the paser and then dry.

109882/1 696

Claims (15)

Claims. 1. New monoazo dyes of the formula Y-R-N = N-D-Y wherein Y-R is a benzene or naphthalene radical containing sulfonic acid groups, Y-D is the remainder of a coupling component of the benzene series or the heterocyclic series, Y is a hydrogen atom and the other Y one over an amino bridge, in particular over an amino bridge of the formula -NH- bonded triazine radical of the formula N / ^ y. CH ₀ -CH ₀ —Co— W ^ N) Ii \ N) H ₀ -CH ₂ / C mean in which A is a quaternized amino or hydrazino group the formula -N-CH ₀ -CH ₀ -N or -N-ITH * * ν 2 2 S 'ν; / XJH ₀ -CH / / X X represents wherein X "represents an anion. 2. monoazo dyes according to claim 1, characterized in that they of the formula 109882/1696 CH-CH_ N SO "H / 2 2 \ j? \ / s / 3 O NC C-NH- \ JH -CH ^x j Il ^ά NN (S "O" H) _ - 3 n — 1 correspond, in which Pz is a 5-pyrazolone radical in the 4-position is bound to the azo bridge, η is an integer in the value of at most 2 and A a grouping of the formula or _ / "chI-ch, X ^ X mean in which X is an anion. 3. monoazo dye according to claim 1, characterized in that that they are of the formula • B ™ * —YY, \ E ^{/ As / N} JtH-C CN IB NJH ₀ -CH / HN ^ ^d I ' correspond, where B is a low molecular alkoxy group, a low molecular weight alkyl group or a hydrogen atom, E is a low molecular alkoxy group, a low molecular weight / or a hydrogen atom / Alkyl group, a low molecular weight alkylamino group 109882/1696 Sulfobenzene or sulfonaphthalene, especially a trisulfonaphthyl radical and A is a grouping of the formula ₃ ,>, N-CH ₂ -OH ₂ -N or -N- X ^CH 3 X ± mean in which X is an anion. 4. monoazo dyes according to claim 2 / wherein Pz is a sulfonic acid group-containing 5-pyrazolone radical, which in I 4-position is bound to the azo bridge. 5. monoazo dyes according to claim 3 * wherein B is a Hydrogen atom and E an acetylamino or ureido group mean.. 6. monoazo dyes according to one of claims 3 and 5 * characterized in that Z is a ß-position on the azo bridge Bound di- or trisulfonaphthy! grouping represents. 7- monoazo dyes according to one of the preceding f Claims, wherein A is a grouping of the formula X ~ CH, \ / ³ —N — CH, represents, wherein X ~ is an anion. 109882/1696 8. Process for the preparation of monoazo dyes of the formula (I) 'Y-R-N = N-D-Y wherein Y-R is a benzene or naphthalene radical containing sulfonic acid groups, Y-D is the radical of a coupling component of the Benzene series or the heterocyclic series, one Y is a hydrogen atom and the other Y is an amino, bridge, in particular via an amino bridge of the formula -NH-bonded Triazine radical of the formula —Σ c — ν ο H I Nm-CH / NN ^ά ■ ^ά
\ // ι · mean in which A is a quaternized amino or hydrazino group the formula CH, -N-OH, -N> , -N-CH-CH-N or -N-NH ";~; ^X ch ₅ -ch / y \ I I - I j X X XX represents, in which X ~ denotes an anion, characterized in that that one can obtain a diazo compound from an amine of the formula YR-NH ₂
wherein Y and R have the meaning given, with a 109882/1696 Coupling component HD-Y combined, in which D and Y have the meaning indicated, or that a dye of the formula (I) indicated, in which all symbols with the exception of A have the meanings indicated and A is a halogen atom, in particular a chlorine or bromine atom , with trimethylamine, pyridine, diazabicycloootane (2 _J 2.2) or dimethylhydrazine. 9 «Process for the production of monoazo dyes of the • p Formula _Z _ _{N = N} A. N , / H ₂ -CH _2x : η C-NO I. Il N) H ₀ -CH / N N ^{2 2} where B is a low molecular alkoxy group, a low molecular weight An alkyl group or a hydrogen atom, E a low molecular weight alkoxy group, a low molecular weight alkyl group, a low molecular acylamino group or a hydrogen atom, Z is a sulfobenzene or sulfonaphthalene radical and A is a group of the formula CH "CH. CHp CH " -N-CH, -N>, -N-CH ₀ -CH ₀ -N ! XI Ή. /; \ cH ₃ X ₁ XXX " represent, in which X ~ denotes an anion, characterized in that a dlazotierten amine of the formula Z-NHp with a compound the formula 109882/1696 H (Y N CH-CH ₀ Il // \ / 2 2 \ —C C — NO I! IN) H -CH /
NN ^ ^ Couples or in particular an azo dye of the formula given, in which, however, A represents a bromine or especially chlorine atom, reacts with trimethylamine pyridine, diazobicyclooctane ^, 2,2) or dimethylhydrazine.
10. Process for the preparation of monoazo dyes of the formula CH-CH ₀ N S0 "H 0 N-C C-NH hi / ⁰ ^ N = N-Pz) I / Ν N (S0_H) _ N ^ _0/3 ^y nl where Pz is a 5-pyrazolone radical which is attached to the azo bridge in the 4-position is bound, η denotes the numbers 1 and 2 and A has the meaning given, characterized in that one diazotized amine of the formula CH ₀ -CH ₀ N
/ 2 2 \ // \ 0 NC C-NH / j II with a connection H-Pz or in particular one 10 9882/1696 Azo dye of the formula given, in which, however, A is a bromine or, in particular, chlorine atom, with trimethylamine, Pyridine, diazobicyclooctane (2,2,2) or dimethylhydrazine implements. 11. The method according to claim 10, characterized in that a 5-pyrazolone, preferably one containing sulfonic acid groups 5-pyrazolone used as a coupling component. 12. The monoazo dyes obtained according to any one of claims 8 to 11. | 13. Process for dyeing textile materials, in particular of cellulosic textile materials using the dyes defined in claims 1 to 7. 1 ^. Process for printing naphtholized cellulose fabrics, characterized in that dyes according to any one of claims 1 to 7 are used. 15. The colored according to one of claims IjJ and 14 or printed textile materials. | 109882/1696